Certain non-ionic surfactants and method of making same



United States Patent CERTAIN NON-IONIC SURFACTANTS AND METHOD OF MAKING SAME Melvin De Groote, University City, and Owen H. Pettingill, Kirkwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application February 7, 1955 Serial No. 486,674

19 Claims. (Cl. 260-2) orn- -cn,-oH-om The present invention then is concerned with a broad genus which may, for sake of convenience, be divided into two subgenera, to wit, a water soluble sub-genera and a water insoluble sub-genera. The solubility, for purpose of convenience, will be defined as ability to dissolve in or mix with distilled water at 23.5" C. instead of at least 5% or thereabouts. Thus, 2-methyl-2,4- pentanediol may be looked upon as a species of the water soluble sub-genera. See our cO-pending application, Serial No. 486,675, filed February 7, 1955. See also, Serial Nos. 486,671; 486,672; and 486,673, filed Febru ary 7, 1955. 1 i

The procedure involved is concerned with treating the" selected diol or the oxyethylated derivatives thereof which have been subjected to threshold oxyethylation (not over 4 moles of ethylene oxide per mole of glycol) to reaction with butylene oxide or propylene oxide or a mixture of the two so that the resultant product is water insoluble, followed by the addition of enough ethylene oxide so the final product shows reduced hydrophobe properties, and in many instances is surface active and preferably so in aqueous solution.

Numerous glycols or ether glycols have been subjected to oxyalkylation with various monoepoxides having not over 4 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, etc. Although the mechanism of oxyalkylation has been studied extensively the mechanism is still a matter of speculation. It is generally agreed that oxyalkylation is comparable to many conventional esterifi cation methods in that it takes place only at a primary or secondary hydroxyl group and it does not take place ordinarily at a tertiary hydroxyl group.

It is true that some compounds and particularly those of a more complicated structure and having a tertiary hydroxyl, have been subjected to oxyalkylation. In such instances there is a possibility that a rearrangement or reaction takes place and that oxyalkylation does not take place at a tertiary hydroxyl radical. Alphaor betaterpineol may illustrate such situation. In some instances dehydration may take place and the mole of water split off may become susceptible to oxyalkylation. In light of present knowledge it seems that when a glycol having a tertiary hydroxyl group is subjected to oxyalkylation that oxyalkylation does take place exclusively at the hydroxyl position other than the tertiary hydroxyl.

Reexamining the formula of one of the diols as hereafter referred to, to wit, 3-methyl-1,3-butanediol the formula. of which is as follows:

CHr-C-CHPC H QH or hexane diol (both the hydroxyl groups being primary.

or secondary) indicated thus, HOROH, and subjects such diol to oxyalkylation, for instance, oxypropylation one would obtain a product indicated thus;

, Actually one obtains a cogeneric mixtureas is well known. In such formula n represents a small whole number or a larger number such as 10 to 20, or an even larger number, such as 30 to 50; In any event, both occurrences of n, and this would refer to the average value, are approximately, the same.

If one then oxyethylates such compound the resultant product can be indicated thus: i

occurrences of n areappr'oximately the If one starts with a pentaneg'lycolsuch as 3-methyl-.

1,3-butanediol the, initial-product using the same amount.

assuming the same amount of ethylene oxide was used. In other words, 3-methyl-1,3-butanediol yields essentially a, nonsymmetrical derivative and for practical purposes Patented June 17, 1958 '3 acts during oxyalkylation as if it were a 'monohydric alcohol and yet has a peculiar property involving hydrophobe-hydrophile balance due to the terminal hydroxyl radical.

There is little or no difference involved in the oxyalkylation of a monohydric alcohol or a dihydric alcohol. A dihydric alcohol if difunctionally reactive oxyalkylates more rapidly as a rule. However, for practical purposes one can oxyalkylate 3-methyl1,3-butanediol in the same manner as if one were oxyalkylating a glycol which is difunctionally reactive. Therefore, in spite of the fact that this particular pentaneglycol reacts from the oxyalkylation standpoint as a higher boiling monohydric alcohol, yet for convenience reference is made to the oxyalkylation of glycols. It should be borne in mind that one might require a somewhat higher temperature or somewhat longer reaction period, or a somewhat increased amount of catalyst to react the same amount of oxide in the same time period as a difunctional glycol but no longer than a comparable monohydric alcohol. Attention is directed to the fact that when large amounts of an alkaline catalyst are used, for instance, 3% to 10% of caustic soda, oxyalkylation may take place at the ter tiary hydroxyl radical.

In an oxyalkylation procedure of the kind herein described particularly since a multiple oxyalkylation is involved (i. e., oxyalkylation with at least 2 different oxides) it is well known that one does not obtain a single compound but a cogeneric mixture. Indeed, this is true of even the simplest oxyalkylation as, for example, the oxyalkylation of a monohydric alcohol. Reference is made to U. S. Patent 2,679,513, dated May 25, 1954, to De Groote with particular reference to columns 19 and 20.

More specifically then, the present invention is concerned with a cogeneric mixture of oxyalkylation derivatives of a member of the class consisting of glycols in which one hydroxyl group is tertiary and the other hydroxyl group is primary or secondary and low stage oxyethylation products thereof, said low stageoxyethy'lation step involving not more than 4 moles of ethylene oxide per mole of glycol, followed by conversion into a surface active mixture being by virtue of a first stage oxyalkylation involving (a) At least one member of the class consisting of propylene oxide and butylene oxide and a second stage oxyalkylation involving (b) Ethylene oxide;

said intermediate prior to oxyethylation being characterized by water insolubility; said final product being characterized by the fact that hydrophobe property of the intermediate is offset to a significant degree by the final stage oxyethylation; the average theoretical molecular weight of said cogeneric mixture being not over 10,000 and not less than 400.

For purpose of convenience What is said hereinafter will be divided into eight parts:

Part 1 is concerned with the description of suitable glycols in which one hydroxyl radical is tertiary and the other hydroxyl radical is either primary or secondary;

Part 2 is concerned with the oxyethylation of a glycol of the kind described in Part 1, preceding if the glycol after threshold oxyethylation is being employed in combination with either butylene oxide or propylene oxide, or both;

Part 3 is concerned with the oxypropylation of a glycol of the kind described in Part 1, or an oxyethylated derivative thereof as described in Part 2, preceding;

Part 4 is concerned with the oxybutylation of a glycol of the kind described in Part 1, preceding, or the oxyethylated derivatives described in Part 2, preceding;

Part 5 is concerned with the oxyalkylation of a glycol of the kind described in Part 1, preceding, or the oxyethylated derivatives described in Part 2, preceding, by means of a mixture of propylene oxide and butylene oxide or for that matter by means of the simultaneous introduction of the two oxides;

Part 6 is concerned with (a) the oxybutylation of the previously described oxypropylated derivatives as appear in Part 3, or (b) the oxypropylation of the previously described oxybutylated derivatives as appear in Part 4;

Part 7 is concerned with the oxyalkylation of the products described in Part 3, 4 or 5, preceding, to give products in which the hydrophobe characteristics have been re duced or offset to a significant degree and which are frequently surface active, particularly in aqueous solution, and

Part 8 is concerned with uses for the products herein described, either as such or after modification.

PART 1 Patent Number Dated Inventor January 16, 1945' Arundale' and Mikeska. Wil es Smith. Bergmann. September 1, l953 Young.

Certain general procedures may be employed which give a variety of suitable glycols, for instance, aforementioned U. S. Patent No. 2,650,940 describes a process for the manufacture of glycols which comprises heating an epoxide of the general formula 806 described the production of tertiary-secondary glycols of the following general formula in which R R and R are monovalent hydrocarbon radi cals, and R is preferably methyl; R and R can. be separate alkyl groups or with the adjacent C atom can form part of a hydroaror'natic ring. I

One exam leof a suitable diol so obtained is 3;,5-di- Arundale and Mikes'ka'.

methyl-hexane-2,3-diol. The compound has the following formula:

CH-CH; H C C- CHl Gets a (o Aforementioned U. S. Patent No. 2,471,391 describes certain procedures in which esters may be obtained which may be hydrolyzed to give suitable diols. As stated in the pat ent: 7

It has been discovered that the 1,3-alkanediols of their ester derivatives may be prepared in an improved efiicaceous manner by reacting a 1,1,3-triacyloxyalkane with hydrogen in the presence of a suitable hydrogenation catalyst and under effective conditions of temperature of reaction and pressure of hydrogen. The reaction of the 1,1,3-triacyloxyalkane with hydrogen has been found to form directly and in a single step esters of l,3-alkanedioles, according to the equation which esters, if desired, then may be hydrolyzed in any known manner to obtain the free glycols of the formula CHI (CHahCHCHzC-OH The structure of the first of The structure of the second one is as follows:

H OH

Other procedures involve the use of a triol such as 2,5- dimethyl-1,2,6-hexanetriol, of the formula Subjecting the same to monoalkylation so as to convert one of the primary terminal hydroxyl radicals into a methyl, ethyl or propyl radical will yield a compound of the formula Examination of such diols and particularly when their alkyl groups appear, for instance butyl, amyl, hexyl, or octyl, and more particularly phenyl or cyclohexyl, it is apparent there are available a variety of such glycols which are water insoluble and particularly those which have 12 to 22 carbon atoms. Not infrequently the pres ence of 8 to 10 carbon atoms is enough to make the product water insoluble. In such instance water insolubility is related to the structure as well as the carbon atom content to say nothing of the presence or absence of an ether oxygen atom. Water solubility in this instance refers more specifically to the test previously noted. Of the two classes of glycols, to wit, those which are water soluble and those which are water insoluble, our preference is to employ the water soluble glycols. Indeed, the preferred water soluble glycol, as previously noted, is 2-methyl-2,4-pentanediol which is the subject matter of the specific invention of our co-pending application, Serial No. 483,413, filed January 21, 1955. Thus in the present instance our preference is to employ the typical glycols of the kind exemplified by the formulas indicated by (a), (b), (c), (d), (e) and (f), none of which have more than 10 carbon atoms. 7

PART 2 As pointed out previously, of the available diols of the kind herein specified the one which is preferred is 2-methyl-2,4-pentanediol. This is the subject matter of a separate application, or applications as referred to previously. In the instant case any one of a number of other diols are equally satisfactory and a perfectly suitable example is 3-methyl-1,3-butanediol. This will be used in a complete series to illustrate the various rami "7 fications. It is understood however that any one of the other herein described glycols, whether having morev than 8 carbon atoms or less than 8 carbon atoms, may be employed.

Thus, one may use not only the herein described diols but it is to be noted that valuable products are obtained also by initial or threshold oxyalkylation, particularly oxyalkylation. involving. not more than-4 moles and preferably one or 2 moles of ethylene oxide per mole of 3- methyl-1,3-butanediol or any other of the herein described glycols having one tertiary hydroxyl radical and the other hydroxyl being either primary or secondary.

It is pointed out in the subsequent parts of this specification, particularly .Parts 3, 4, 5 and 6, that prior to the final oxyethylation the intermediate should be substantially water insoluble and preferably soluble in xylene, kerosene or a mixture of the two. Needless to say, if ethylene oxide is used for threshold oxyethylation a larger abount of the other oxides, i. e., either propylene oxide or butylene oxide or the two in combination must be employed to obtain the desired solubility as indicated above.

The oxyalkylation of various glycols, such as ethyleneglycol, propyleneglycol, butyleneglycol, or the like with various oxides and particularly alpha-beta olefinic oxides having 4 carbon atoms or less, has been described in the literature. Instead of using ethylene oxide one can, of course, use ethylene carbonate. Likewise, propylene carbo'nate may be used.

As is well known the oxyethylation derivatives from any oxyalkylation susceptible compound are prepared by the addition reaction between ethylene oxide and such compound. The addition reaction is advantageously carried out at an elevated temperature and pressure and in the presence of a small amount of alkaline catalyst. Usually, the catalyst is sodium hydroxide or sodium methylate. Metallic sodium with-the prior elimination of hydrogen (formation of an alkoxide) can be used. The reaction temperature is apt to be 150 C. or somewhat less, and the reaction pressure not in excess of 30 to 60 pounds per square inch. The reaction proceeds rapidly. Actually,there.is very littledifiference between the use of propylene oxide and ethylene oxide or, for that matter straight chainbutylene oxide, and either one of the. two other oxides. See, for example, U. S. Patent No. 2,636,038 dated April 21, 1953, to Brandner, although another hydroxylated compound is employed.

As to further information in regard to the mechanical steps involved in oxyalkylation, see U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote et al. Partieular' reference is made to columns 92 et seq.

- The oxyethylation of a liquid or a solid which can be melted at comparatively low temperature (under 150 C.) without decomposition or is soluble in an inert solvent, such as xylene, presents little or no mechanical difficulties inthe oxyal-kylation step. When one has a solid which cannot be melted, or decomposes on melting, and is insoluble in xylene, a slurry may be employed as in the case of the oxyalkylation of sucrose. See U. S. Patent No. 2,652,394, dated September 15, 1953, to De Groote. Actually, as far as oxyalkylating a slurry of a xylene-insoluble solid in xylene the procedure is substantially the same for pentaerythritol, or sorbitol, or sucrose, or for that matter, for glucose, or a solid amine such as tris(hydroxymethy1)aminomethane, or 3-methyl-1,3-butanediol or a-nyother of the herein specified glycols.

However, the oxyalkylation of 2-methyl-1,3-butanediol is comparatively simple for the reason that both hydroxyl groups are primary and the product, although a solid at ordinary temperature, is a liquid at a convenient oxyalkylation temperature, for instance 130 C., or less. Thus, one can do either one of two things; mix the product aromatic solvent so as to produce a solution or slurry or else simply melt and have the product liquid priorltov introduction of the oxide. Our preference is simply to mix the product with a suitable amount of a selected catalyst such as powdered caustic soda or powdered sodium methylate. The amount of catalyst may vary from 1% to 5%. The reaction vessel is flushed out and the temperature raised to an appropriate point and one then proceeds with oxyethylation in the customary manner. In any event whether one adds a solvent or suspending medium, or merely melts the product it is immaterial because at a very early stage the material becomes a liquid even at ordinary temperatures and becomes homogeneous by solution, or better dispersion. In essence, it is immaterial whether one starts with a slurry, an emulsion, a." suspension, or a solution. It is also immaterial if one starts with a solid in absence of any liquid provided only that the product is not decomposed and is a liquid at oxyalkylation temperature. This is true of 3-methyl-1,3-butanediol as previously pointed out.

As to the oxyalklation of a glycol see also U. S. Patent No. 2,674,619 dated April 6, 1954, to Lundsted.

It is not believed any examples are necessary for the reason that the oxyalkylation and particularly limited oxyalkylation of the kind herein described is identicalfor all purposes with the oxyethylation of ethylene glycol or diethyleneglycol.

For purpose of illustration the following examples are included.

' I Example 122 The reaction vessel employed was a stainless steelauto} clave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., which are conventional in this type of apparatus. The capacity was approximately 5 liters. The stirrer operated at a speed of approximately 250 R. P. M. i

There were charged into the autoclave 2080 grams of 3-methyl-1,3-butanediol, and 25 grams of sodium methylate. The autoclave was sealed, swept with nitrogen gas and heat applied, with stirringv started as soon as the product became fluid. The temperature was allowed to rise to approximately 142 C. At this particular time the addition of ethylene oxide was started. It was added continuously at such speed that it was absorbed by the reaction as added. The amount added in this operation was 880 grams. The time required to add the ethylene oxide was 1% hours. During this period the temperature was maintained at 138 C. to 154 C., using cooling water through the inner coils when necessary and otherwise applying heat if required. The maximum pressure during the reaction was 55 pounds per square inch. This represented the' addition of 20 gram moles of ethylene oxide to 20 gram moles of 3-methyl-1,3-butanediol, i. e., a oneto-one molal ratio. The theoretical molecular weight of the various examples will be indicated by figures in parentheses at the end of each example.-

Example 2a After withdrawal of the product identified as Example 1a, above, the autoclave was recharged and the procedure repeated but in this instance the amount of ethylene oxide 1 added to the 2080 grams :of 3-methyl-l,3-butanediol was Example 3a Using a similar procedure as in Examples 1a and 2a,

and a slightly larger autoclave, 7 /2 liters capacity, 264

Example 4a The same larger size autoclave was employed as in Example 3a, preceding, and the amount of oxide added to the same amount of 3-methyl-1,3-butanediol was 3520 grams. This represented a 4-to-1 molal ratio as compared to a 3-to-1 molal ratio in the preceding example. The amount of sodium methylate used was 40 grams, the time required for oxyethylation was about 3 hours, and the conditions as far as temperature and pressure were concerned were the same as in the preceding example. (280 M. W.)

PART 3 In light of the fact which has been pointed out previously propylene oxide reacts with substantially the same ease as ethylene oxide, although sometimes requiring slightly higher temperatures, or slightly higher pressures, or slightly longer reaction period so the difference is only one of a rather slight degree if any. This is illustrated by a large number of patents which describe such oxyalkylation procedure.

Oxypropylation or oxybutylation sometimes has one advantage. If the mixture is water soluble, such as 3- methyl-l,3-butanediol or oxyethylated 3-methyl-1,3-butanediol, and if a solvent is employed, initial oxybuytlation or low stage oxypropylation soon produces a xylene soluble derivative and thus the mixture becomes truly homogeneous by solution at an early stage in oxyalkylation. 1

Previous reference has been made to our co-pending application, Serial No. 486,675, filed February 7, 1955. What is said hereinafter is substantially the text comparable to what appears in said co-pending application.

It is again to be emphasized that 3-methyl-1,3-butanediol is simply one example of a group of compounds, some of which have more than 8 carbon :atoms or less, in which there are 2 hydroxyl groups, one of which is tertiary and the other either primary or secondary. Any such glycols can be substituted on a mole-for-mole basis or in the instance of the lower molal products having 10 carbon atoms or less on a weight-for-weight basis, in any of the oxyalkylation procedures described in the present specification, and not limited to this particular part, so as to yield the same analogous products which collectively characterize the present invention.

Example 1b The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., which is conventional in this type of apparatus. The capacity was approximately 4 liters. The stirrer operated at a speed of about 250 R. P. M.

There were charged into the autoclave 520 grams of 3-methyl-1,3-butanediol and 60 grams of sodium methylate. The autoclave was sealed, swept with nitrogen gas and stirring started immediately, and heat applied. The

temperature was allowed to rise to approximately 152 C. At this particular time the addition of propylene oxide was started. Propylene oxide was added continuously at such speed that it was absorbed by the reaction as added. The

amount of propylene oxide addedwas 1630 grams. The

time required to add the propylene oxidewas one hour.

10 During this period the temperature was maintained at to C., using cooling water through the inner coils when necessary and otherwise applying heat it required. The maximum pressure during the reaction was 46 pounds per square inch. Ignoring the sodium methylate and considering only 3-methyl-1,3-butanediol for convenience, the final pnoduct had a molecular weight of 430.

Example 2b Without adding any more catalyst, the procedure was continued by adding 1560 grams of propylene oxide under substantially the same operating conditions 'but requiring about 3 hours for the addition. (742 M. W.)

Example 3b In a third step, the amount of propylene oxide added was 1670 grams. I he reaction slowed up and required approximately 5 hours, using the same operating temperatures and pressures. (1080 M. W.)

Example 4b The fourth and final oxyalkylation was completed by addition of 1710 grams of propylene oxide, and the oxyalkylation was complete within 5% hours using the same temperature range and pressure as previously. At the end of the reaction the product had a molecular weight of 1418.

Example 5 b In another oxyalkylation the same procedure as indicated in Examples 1b to 4b above, was employed using approximately the same percentage of catalyst, same temperature, and same pressure, but to the initial amount of 3-methyl-1,3-butanediol was added 28.4 parts by weight of propylene oxide. This was a single operation in which the time required was approximately ten hours. The molecular weight of the final product was approximately 3070.

Example 6b Series 10 to 60, inclusive This series is the equivalent of Series 1b through 6b,

with this difierence: instead of using 3-methyl-l,3-bu-,

tanediol as the starting material the mono-molecular ethyleneoxide addition product designated as Example la, was used as the starting material. However, instead of using 3-methyll,3-'butanediol as the initial reactant there was used instead a molal equivalent of the product identified as Example 1a. This product had a molecular weight of 148 instead of 104, and thus, for example, in the preparation corresponding to Example lb instead of using 520 grams of the initial reactant the amount was increased by 42%, i. e., the amount used was 740 grams. The arnount of propylene oxide added was varied slightly so that the final molecular weight would be approximately the same as in the Example lb series. More specifically the catalyst which was present in Example 1a from 11 l 1 the oxyethylation stage was permitted to remain and more catalyst was added as in the 1b6b series, without making anychange due to the addition. of the previously present catalyst.

In some instancestitration after exhaustive oxyalkylation showed that part of the alkaline catalyst, whether caustic soda or sodium methylate, apparently was expended in combination with a trace of acidic material formed in some obscure manner. In procedures where an oxyalkylated product was then subjected to further oxyalkylatio-n the total amount of catalyst indicated as, for example, in subsequent Table I, is based on the amount added plus the value of titration as a rule, rather than based on calculated residual alkaline catalyst.

The time factor, and temperature employed, and the pressure used, all were substantially the same as in corresponding examples in the 1b-6b series. (474; 789; 1129; 1464; and approximately 4200 to 4620, M. W., respectively.)

Series 1d to 6d, inclusive This series was comparable to the 1c6c series described above except that the initial material was the product identified as Example 2a, and instead of using 520 grams of 3-methyl-1,3-butanediol there were used 860 grams of oxyethylation derivative Example 2a. The presence of catalyst was ignored as previously, and the operating conditions were substantially the same as before in regard to time, temperature, pressure, etc. Here, again, the amount of propylene oxide added was varied slightly so the molecular weights were approximately as before, to wit, 518; 834; 1174; 1500; and approximately 5350 to 7940, respectively. 7

PART 4 As in Part 3, preceding, reference is made in this instance, to our co-pending application, Serial No. 486,675, filed February 7, 1955, and much of what is said herein is in essence the verbatim text as it appears in said co-pending application, except of course that in the present instance for purpose of illustration the particular initial reactant is 3-methyl-1,3-butanediol, whereas in said aforementioned co-pending application it was 2-methyl- .2,4-pentanediol.

At the present time there is available butylene oxide which includes isomericlmixtures; for instance, one manufacturer has previously supplied a mixed butylene oxide which is in essence a mixture of l-butene oxide, 2-butene oxide isomers and approximately 10% isobutylene oxide. Another manufacturer has supplied an oxide which is roughly a fifty-fifty mixture of the cisand trans-isomers and 2-butene oxide.

There is also available a butylene oxide which is characterized as straight chain isomers being a mixture of the 1,2 and the 2,3 isomers and substantially free from the isobutylene oxide.

This latter product appears to consist of 80% of the 1,2 isomer and of the mixed 2,3 cisand 2,3-tra'nsisomer. We have obtained the best results by using an oxide that is roughly 80% or more of the 1,2-isomer and with either none, or just a few percent if any, of the isobutylene oxide, the difference being either form of the 2,3 or a mixture of the two forms.

Our preference is to use an oxide substantially free from the isobutylene oxide, or at least having minimum amounts of isobutylene oxide present.

Since the varying solubility of different butanols is well known, it is unnecessary to comment on the effect that the varying structure has on solubility of derivatives obtained by butylene oxide. Purely by Way of example, the applicants have tested the solubility of the first two available butylene oxides and noted in one instance the butylene oxide would dissolve to the extent of 23 grams in 100 grams of water, whereas the other butylene oxide would only dissolve to the extent of 6 grams in 100 grams of water. These tests were made at 25 C.

As to further reference in regard to the isomeric butylene oxides see Chemistry of CarbonCompounds, volume 1, part A, Aliphatic Compounds, edited by E. H. Rodd, Elsevier Publishing Comapny, New York, 1951, page 671. 7

As to the difference in certain proportions of the cisand transform of straight chain isomers 2,3-epoxybutane see page 341 of A Manual of Organic Chemistry, volume 1, G. Malcolm Dyson, Longmans, Green & Com

pany, New York, 1950.

Reference to butylene oxide herein of course is to thecompound or compounds having the oxirane ring and thus excludes 1,4-butylene oxide (tetrahydrofura'ne) .or a trimethylene ring compound. v

- When reference is made to the oxides, for instance, ethylene oxide and butylene oxide, one can use the corresponding carbonates. Ethylene carbonate is available commercially. Butylene carbonate, or the carbonate corresponding to a particular oxide, is not available commerically but can be prepared by the usual methods in the laboratory. For this reason further reference to the alkylene carbonates will be ignored although it is understood when oxyethylation takes place by means of ethylene carbonate one could, of course, use butylene carbonate for oxybutylation.

- In the present invention we have found that outstanding products are obtained by the use of certain preferred butylene oxides, i. e.,-,those entirely free or substantially free (usually 1% or less) and composed of approximately or more of the 1,2-isorne'r with the remainder, if any, beingthe 2,3 isomer.

In the preparation of the outstanding compounds we have studiously avoided the presence of the isobutylene oxide as far as practical. When any significant amount of isobutylene oxide happens to be present, the results are not as satisfactory regardless of the point when the butylene oxide is introduced. One explanation may be the following. The initial oxybutylation which may be simplified by reference to a monohydric alcohol, produces a tertiary alcohol. Thus the oxybutylation in the presence of an alkaline catalyst may be shown thus:

CH: H Y ROH+HC-C CHs alcohol is involved although the literature records suecessful oxyalkylation of tertiary alcohols. This does not necessarily apply when ox'yalkylation takes place in the presence of an acidic catalyst, forinstanc'e, a metallic chloride such as f erric chloride, stannic chloride, aluminum chloride, etc. We are not completely satisfied that oxyalkylation of 3-methyl-1,3-butanediol in presence of an acidic catalyst, after salt formation, may not cause some degradation, possibly etherization or dehydration, to take place. The situation is somewhat akin to sorbitol which involves similar derivatives. Thus, oxyalkylation under such conditions may involve 3-methyl-1,3- butanediol in part and may involve 3-methyl-'1,3-butanediol degradation products in part and also may involve water in part. We have tried procedures such as using 13 an alkaline catalyst and 3-methyl-1,3-butanediol, employing about 4 to 6 moles of isobutylene oxide. Afterwards, an amount of acid was added equal to the amount of caustic used as a catalyst and the reaction mass was dried and then stannic chloride added. Under such circumstances the results suggest more satisfactory oxybutylation as such although the procedure becomes cumbersome, uneconomical and perhaps even impractical. Actually, an acid catalyst or so-called neutral catalyst (clay) can be used with ethylene oxide or propylene oxide as well as butylene oxide.

This, however, seems to be only a partial explanation. Another explanation may rest with the fact that isobutylene oxide may show a tendency to revert back to isobutylene and oxygen and this oxygen may tend to oxidize the terminal hydroxyl radicals. This possibility is purely a matter of speculation, but may account for the reason we obtain much better results using a butylene oxide as specified. In regard to this reaction, i. e., possible conversion of an alkylene oxide back to the olefine and nascent oxygen, see Tall Oil Studies II Decolorization of Polyethenoxy Tallates, with Ozone and Hydrogen Peroxide, U. V. Karabinos et al., I. Am. Oil Chem. Soc. 31, 71 (1954).

For purpose of illustration the following examples are included:

Example 1e The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., which is conventional in this type of apparatus. The capacity was approximately 4 liters. The stirrer operated at a speed of about 250 R. P. M.

There were charged into the autoclave 520 grams of 3-methyl-1,3-butanediol. There were added 60 grams of sodium methylate. The autoclave was sealed, swept with nitrogen gas and stirring started immediately and heat applied. The temperature was allowed to rise to approximately 153 C. At this particular time the addition of butylene oxide was started. The butylene oxide employed was a mixture of the straight chain isomers substantially free from isobutylene oxide. It was added continuously at such speed that it was absorbed by the reaction as added. The amount added in this operation was 1630 grams. The time required to add the butylene oxide was 2 hours. During this period the temperature was maintained at 150 C. to 155 C., using cooling water through the inner coils when necessary and otherwise applying heat' if required. The maximum pres- I sure during the reaction was 51 pounds per square inch.

Ignoring the sodium methylate and considering only 3methyl-1,3-butanediol and butylene oxide the resultant product had a molecular weight of 430.

Example 2e Example 3e In a third step, the amount of propylene oxide added was 1670 grams. The reaction slowed up and required approximately 5 hours, using the same operating temperatures and pressures. (1079 M. W.)

Example 4e The fourth and final oxyalkylation was completed by addition of 1710 grams of butylene oxide and the oxyalkylation was complete Within 6 hours using the same temperature range and pressure, as previously. M. W.)

Example 5 e the time required was approximately 10 hours. The mo lecular weight of the final product was approximately Example 6e The same procedure was followed as in Example 5e, preceding, using the same initial amount of 3-methy1-1,3- butanediol but the amount of butylene oxide added was equivalent to 42.6 parts by weight and the approximate molecular weight of the final product was about 4540.

1 Note in other similar procedures we have obtained products by use of butylene oxide in which the molecular weight ranged from 5.000 to 8500 and which, after subsequent treatment with ethylene oxide, approximated 10,000 or thereabouts.

Molecular weight determination on polyalkylene-glycols present no diffi'culty in the lower molecular weight products; or, for that matter, in the case of glyools having moderate molecular weight, for instance up to 2000, 2500 or even 3000. From the range 3000 to 5000 the results obtained by usual methods are at the most approximate and in a range from 5000 to 8000 to 10,000 they are even less satisfactory. The reasons are well known and thus in many instances it is more feasible to simply base the molecular weight on the average theoretical molecular weight assuming that all the oxide added combined as such and none remained uncombined or lost during the process. Precaution toobtain complete combination has been employed in connection with all examples referred to in the present specification.

Series If to 61, inclusive This series is the equivalent of Series 1e to 4e, with this difference; instead of using 3-methyl-1,3-butanediol as the starting material the mono-molecular ethylene oxide addition product designated as Example 1a, was used as the starting material. However, instead of using 520 grams of 3-methyl-1,3-butanediol as the initial reactant there was used instead 740 grams of the product identified as Example la. The catalyst which was present in Example 1a from the oxyethylation stage was permitted to remain and more catalyst was added as in the 1b-6b series, without making any change due to the addition of the previously present catalyst.

The time factor, and temperature employed, and the pressure used, all were substantially the same as in the corresponding examples in the lb-6b series. (474; 789; 1129; 1464; approximately 2700 to 4000 M. W. respectively.)

Series lg to 6g, inclusive "PART 5 Needless to say, instead of using propylene oxide and anode-7e butylene oxide separately one can employ a mixture of the two oxides; In such event one obtains random oxy- =alkylation with the likelihood that oxypropylation takes place, at least initially, more rapidly than oxybutylation. The rate of reaction would also be affected by the particular butylene oxide selected. What has been said preceding would apply even if one were to use the most reactive butylene oxide, to wit, the straight chain oxide commercially available.

As a matter of fact, one need not mix the two oxides in order to obtain random oxyalkyl-ation but one may employ a reaction vessel in which both oxides can be introduced simultaneously and thus use appropriate input rates to furnish the required amount of oxide. We have found no advantage in random oxyalkylation for any one of a number of reasons that are obvious. The first is that butylene oxide costs more than propylene oxide and if the same result can be obtained by the use of propylene oxide we prefer to use propylene oxide purely as a matter of economy. Secondly, where we have used butylene oxide'the best results are obtained by introducing the butyle'ne oxide without the simultaneous introduction of propylene oxide. However, we have prepared various series of compounds in which the ratio of propylene oxide and butylene oxide varied. In one series we used a mixture of equal parts by weight. Our preference has been a mixture containing 90% propylene oxide and butylene oxide by weight. Even in this instance it is questionable that there is justification for using the mixture rather than each oxide separate. However, it is to be noted they were prepared fromneopentyl glycol and also from the product previously identified as Example 1a, and also from the product previously identified as Example 2a. Derivatives were prepared in which the average molecular weight corresponded roughly to the Examples lb through 6b series, to wit, the lowest of the stages being as follows:

Approximately 400, approximately 725, approximately 1-050,-approximately 1400, approximately 2500 and approximately 3850. Such derivatives were treated with ethylene oxide in the same way as the comp-arable procedure described in Part 6 which appears subsequently.

16 For reasons pointed out previously details of such data will be omitted, but the products can be readily reproduced in light of the above information.

'PART'6 The products derived in the manner described in Parts 2, 3, or 4 are suitable for oxyethylation in the manner described in Part 6 in order to produce the compounds of the present invention. However, if desired one could react the oxypropylated products derived in Part 2 with butylene oxide and then subject such intermediate to reaction with ethylene oxide. Likewise, one could subject the oxybutylated products derived in the manner described in Part 3 to oxypropylation and then treat with ethylene oxide. For that matter one could take the products obtained by random oxyalkylation as described in Part 4 and treat further with either butylene oxide or propylene oxide and then follow with ethylene oxide. Also, one could take the products obtained by random oxyalkylation as described in Part 4 and treat further with either butylene oxide or propylene oxide and then follow with ethylene oxide. For reasons set out in Part 4, for the purpose of preparing other variants, this applies equally well to any such subsequent oxyalkylation with either propylene oxide or butylene oxide. Therefore, our preference in preparing a double stage intermediate as differentiated from a single stage random oxyalkylation, and as described in the two sections immediately following.

Section A The oxybutylation of the previously described oxypropylated derivatives is in essence the same procedure as appears in Part 3, preceding. Generally speaking, we have found the best results by using such butylation step in connection with fairly low molal oxypropylated derivatives of the kind described in Part 2, preceding. A variety of intermediates have been prepared and reference is made to the tabular summary which appears as Table I, immediately following, and gives complete data as to composition, operational procedure, etc.

TABLE I Prevl- Sodium ously methylate Max. Max. Molec. oxypresent pres. temo, wt. of propyl- Theo. including Total p. s. 1. C. prod. Ex. ated 3- molec. Grams amt. left Oxide Grams time during during after No. methyiwt. 0! over from added period, oxyoxyoxy- 1,3- reactant prior hours alkylalkylalkylbutaneoxyation ation ation d101, alkylstep Ex. No. ations 1i 430 430 BuO 72 145 502 2i 430 430 45 BuO 144 1% 50 145 574 31' 430 430 45 BuO 216 2 50 145 646 4i 430 430 45 BuO 288 3 50 145 718 iii 430 430 45 BuO 432 6 50 145 862 6i 430 430 45 BuO 936 8% 50 145 1, 266 7i 1,080 1, 080 BuO 144 1 50 145 1, 224 81: 1, 080 1, 080 60 B110 216 2 50 145 1, 296 9 474 474 50 BuO 144 1% 50 145 618 10t 474 474 50 BuO 216 2% 50 145 690 11 474 474 50 B110 288 3 50 145 762 12 474 474 50 B110 432 4 50 145 906 13 474 474 50 B110 504 5 50 145 978 14 474 474 50 B110 576 6% 50 145 1, 050 15 789 789 B 216 2% 50 1, 005 789 789 80 B110 432 4 50 145 1, 221 789 789 80 BuO 504 5% 50 145 1, 293 789 789 80 BuO 648 7% 50 145 1, 437 789 780 80 B110 836 9% 50 145 I 625 518 518 55 B110 72 50 145 590 518 518 55 BuO 144 1% 50 145 662 518 518 55 BuO 216 2% 50 145 734 518 518 55 BuO 288 3% 50 145 806 518 518 55 BuO 432 4% 50 145 950 518 518 55 BuO 720 7 50 145 1, 238 834 834 45 B110 216 3 50 145 1, 050 834 834 45 B110 432 6 50 145 1, 266 834 834 45 BuO 504 8 50 145 1,338

May have had threshold treatment with EtO prior to oxy'propylation.

TABLE IV Previ- Sodium ously methylate Max. Max. Molec oxypresent pres. tramp, wt. of propyl- Theo. including Total p. s i. C. prod. Ex. atecl 3- moleo. Grams amt. left Oxide Grams tune during during after No. methylwt. of over from added period, oxyoxyoxy- 1,3- reactant prior hours alkylalkylalkylbutaneoxyntion atlon atiou diol,* alkylstop Ex. No. ations 3, 214 3, 214 160 EtO 88 1 25 135 3, 302 3, 214 3, 214 160 EtO 132 1% 25 1,35 3, 356 3, 214 3, 214 160 EtO 176 2 25 135 3, 390 3, 214 3, 214 160 EtO 264 3 25 135 3, 478 3, 214 3, 214 160 EtO 528 5% 135 3, 732 3, 214 3, 214 160 EtO 616 7 25 135 3, 830 3, 214 3, 214 160 EtO 792 6% 25 135 4, 006 2, 413 2, 413 120 Ett) '14 5 25 135 2, 457 2, 413 2, 413 120 EtO 8S 1 25 135 2, 501 2, 413 2, 413 120 EtO 132 1% 25 135 2, 545 2, 413 2. 41.3 120 EtQ 176 2 25 135 2, 589 2, 413 2, 413 120 EtO 264 p 3 25 135 2,677 2, 413 2, 413 120 EtO 352 4 25 135 2, 765 2, 405 2, 405 120 EtO 528 5 25 135 2, 933 2, 405 2, 405 100 EtO 132 2 25 135 2, 537 2,405 2, 406 100 EtO 176 2% 25 135 2, 58L 2, 405 2, 405 100 EtO 220 3 25 135. 2, 625 2, 405 2,405 100 EtO 264 3% 25 135 2, 669 2,405 2, 405 100 EtO 308 4% 25 135 2, 713 2, 405 2, 305 100 EtO 352 5 25 135. 2, 757 2, 405 2, 405 100 EtO 396 6 25 135 2, 801 2, 830 2, 830 170 EtO 83 1 25 135 2, 918 2, 830 2, 830 170 EtO 132 1% 25 135. 2, 962 2, 830 2, 830 170 EtO 176 2% 25 135 3, 00,6 2, 830 2, 830 170 EtO 220 3 25 135. 3, 050 2, 830 2, 830 170 EtO 264 4 25 135 3, 004 2,830 2,830 170 B110 308 5 25 1 3,138 2, S30 2, 830 170 EtO 352 6% 25 135 3, 182

From series in which butylene oxide was used first and then propylene oxide.

PART 7 This part is concerned with the final oxyethylation step which is used to offset the hydrophobe properties of the intermediate or, stated another way, to introduce hydrophile properties. The intermediate polyalkyleneglycol is essentially water insoluble or at the most water dispersible within the limits previously-stated. Thus, the introduction of any group in which the ratio of oxygen to carbon is comparatively high such as reaction involving one or for certain two or more ethylene oxide groups obviously raises the hydrophile properties, particularly if in a terminal position. M

As such hydrophile properties appear and begin to increase their effect is noticeable and the properties which convert the hydrophobe material into a nonionic surfactant, i. e., the ability to lower the surface tension of a liquid, for instance water or parafiin oil, or to change the interfacial tension at the interface between water and oil and water and some other liquid and by the ability to form emulsions, show dispersion properties show detergent or detergent-like properties. The simhexane, monochlorobenzene, etc.

plest test of all is the ability of the product to disperse in water although at times it is recognized that there may be a profound increase in hydrophile properties before this threshold is reached. In light of these well known properties it is believed the characteristics included in the claims are perfectly obvious to those skilled in the art.

In some of the claims the hydrophile effect is pointed out by reference to dispersibility and in other claims to dispersibility tests involving specific properties.

. Inversely, just as hydrophile effects become obvious by measuring the balance between the hydrophob portion and the hydrophile portion, it also follows that as this balance is inverted the same properties tend to be reduced as, for example, by the oxypropylation of the previously oxyethylated 3-methyl-1,3-butaned iol provided an oxyethylation addition product is used as the initial raw material. Even if it were not, this would be true insofar that 3-methyl-l,3-butanediol is water soluble solvents such 'as esters, alcohol, ethers, etc. ethylated derivatives do show at least some hydrophile at ordinary temperatures; In any event, there is no difficulty in noting qualitatively and perhaps to some extent perhaps semiquantitatively the change in characteristics as ethylene oxide is introduced into the intermediate derivative.

In recapitulation of what has been said previously the following justifies brief emphasis. The intermediate is water insoluble within the limits previously set forth. It is soluble in a number of organic solvents such as hydrocarbon solvents including aromatic petroleum solvents, aliphatic petroleum solvents, coal tar derived aromatic solvents and the like. Similarly, it is soluble in organic solvents such as carbon tetrachloride, n-heptane cyclo- It is also soluble in a large number of oxygenated solvents such as acetone, ether, ethanol, methanol and a number of higher alcohols. In some instances the products show solubility in mixtures of nonoxygenated organic solvents, oxygenated organic solvents having a common solvent efiect, and a small amount for instance, a few percent, of water.

After the final oxyethylation the final product so obtained is likewise soluble in a variety of organic solvents such as those previously mentioned along with other Such oxyproperties and frequently enough show solubility in water as, for example, a dilute solution of 1% to 5% in distilled water of 22.5 C., and at times even solubility in water in the presence, of a significant amount of inorganic salts such as sodium sulfate. Here, again, the product is readily' soluble in a number of solvent mixtures and in numerous cases in amixture of the kind previously described containing a small amount of water.

It has been previously pointed out that oxyethylation introduces a. hydrophile-hydrophobe balance which is shifted backwardat least somewhat, in light of the fact that the initial reactant 3-methyl-1,3-butanediol or oxyethylated 3-methyI-L3-butanediol, had initial hydrophilo characteristics whereas the intermediate prior to oxyethylation had predominant hydrophobe characteristics. In the claims it "has been pointed out that one could mix or shake one to five parts of the oxyalkylated derivatives, or thev product derived therefrom by oxyproease-. 78;

21 pylation, with 99 to 95 parts of water at-;22-.5 C. and note the change in hydrophile or hydrophobe properties. Actually, the tests can be conducted without following these specific ratios. ,Indeed, a few drops of the organic derivatives in distilled water or tap water will serve. Not only that, the presence of a foam or absence of a foam is another quick test for the. appraisal ofthe surtion employing a combination of propylene oxide andbutylene oxide can be oxyethylated to give another series comparable to or analogous to those described and including as part of the present invention. For sake of brevity and also for reasons set forth elsewhere specific data are not included.

If the final oxyalkylated glycol derivatives are obtained factant properties previously specified. by means of an alkaline catalyst which is the usual pro- TABLE v Prevl- Sodium ously methylate Max. Max. Moiec. oxypresent pres. torrid) wt. oi propyl- Theo. including Total p. s. 1. prod. Ex. ated 3- melee. Grams amt. leit Oxide Grams time during during alter N0. methylwt. of over irom added period, oxyoxyoxy- 1,3- reactant prior hours alkylalkylalkyloxyation ation ation alkylstep ations 1, 418 1, 418 140 EtO 44 K 25 135 1, 462 1, 418 1, 418 140 E $4 135 1, 566 1, 418 1, 418 140 EtO 132 1% 25 135 1, 550 1, 418 1, 418 140 EtO 176 2% 25 135 1, 594 1, 418 1, 418 140 EtO 264 3% 25 135 1, 682 3, 070 1, 535 270 EtO B8 25 135 3, 246 3, 070 1, 535 270 EtO 132 1% 25 135 3, 334 3, O 1, 535 270 EtO 176 2% 25 135 3, 3, 070 1, 535 270 EtO 264 3% 25 135 3, 598 3, 070 1, 535 270 EtO 308 4% 25 135 3, 686 3, 070 270 EtO 396 5 25 135 3, 862 -3, 070 1, 535 270 EtO 616 25 135 4, 302 3, 070 1, 535 270 EtO 792 8% 25 135 4, 654 4, 540 2, 270 200 EtO 1 25 135 4, 716 4, 540 2, 270 200 EtO 176 2 25 135 4, 892 4, 540 2, 270 200 EtO 220 3 25 135 4, 980 4, 540 2, 270 EtO 396 4% 25 135 5, 332 4, 540 2, 270 260 EtO 616 7% 25 135 5, 772 4, 200 2, EtO 1 25 135 4, 376 4, 200 2, 100 i 135 EtO 132 1% 25 135 4, 4 4, 200 2, 100 135 EtO 176 25 135 4, 552 4, 200 2, 100 135 EtO 220 4% 25 135 4, 640 4, 200 2, 100 135 EtO 264 5 25 135 4, 728 4, 620 2, 310 200 EtO 132 2 25 135 4, 4, 630 2, 310 200 EtO 176 3 25 135 4, 972 26m.. 4, 630 2, 310 200 EtO 220 3% 25 135 5, 060 27m- 4, 630 2, 310 200 EtO 264 4% 25 135 4, 158 28111..-- 4, 630 2, 310 EtO 308 25 135 5, 236

From series using propylene oxide only, to wit, the 15 65 series, 1c6c series, and the 11144 series.

TABLE VI Prevl- Sodium ously methylate Max. Max. Moleo oxypresent pres. temp., wt. of propyl- Theo. including Total s. 1. 0. prod. Ex. ated 3 moles. Grams amt. lei't Oxide Grams time uring during after No. methylwt. of 7 over from added period, oxyoxyoxy- 1,3- reactant prior hours alkylalkylelkylbutaneoxyation atlon ation 01, alkylv step Ex. No. ations 1, 079 1, 079 107 EtO 132 1 25 135 1, 211 l, 079 1, 079 107 15170 264 2 25 135 1,3 1, 079 1, 079 107 EtO .396 3% 25 135 1, 475 1, 079 1, 079 107 EtO 528 4% 25 135 1, 607 1,079 1,079 107 EtO l, 056 8% 25 135 2, 135 1,419 1, 419 EtO 264 2 25 135 1, 683 1, 419 1, 419 140 EtO 396 3% 25 135 1, 815 1,419 1,419 140 EtO I 792 25 135 2,211 1, 419 1, 419 140 END 1, 056 7% 25 135 2, 475 1, 419 1,419 140 EtO 1, 584 25 135 3, 003 3, 070 3, 07,0 135 EtO 264 2 25 135 3, 334 3, 070 3, 070 135 .EtO 396 25 135 3, 466 3, 070 3, 070 135 E120 792 4% 25 135 3, 862 3, 070 3, 070 135 EtO 1,056 25 135 4, 126 3, 070 3, 070 135 EtO 1, 584 9% 25 135 4, 654 1, 464 1, 464 EtO 132 25 135 1, 596 1, 464 l, 464 145 EtO 264 1% 25 135 1, 728 1, 464 1, 464 145 EtO 396 25 135 1, l, 464 1, 464 145 EtO 484 4% 25 135 1, 948 l, 464 l, 464 145 EtO 968 7 25 135 2, 432 1, 679 1, 679 167 EtO 396 3 25 135 2, 075 1, 679 l, 679 167 EtO 792 5 25 135 2, i, 679 1, 679 167 EtO 1, 056 25 135 2, 735 1, 679 1, 679 167 EtO 1, 584 4 9% 25 135 3, 263 2, 700 2, 700 135 E50 264 25 135 2, 9 2, 700 2, 700 135 EtO 396 3% 25 135 3, 096 2, 706 2, 700 135 EtO .792 5 25 135 3, 492 2, 700 2, 700 135 EtO 1,056 7% 25 135 3, 756

From series using butylene oxide only, to 'wit, the le-fie series, 1H5] series, and la-Sg series.

.It is unnecessary to pointout that products of the kind cedure, then if the residual alkaline catalyst is not redescribedin Part' '4 and obtained hyrando1n o ryalkyla- 75 moved, for. example, there may besome wastage of the.

derivatives, along with the formation of inorganic salt of the acid which remains at an undesirable impurity.

The preference is to remove such alkaline catalyst by any conventional method. See U. S. Patent No. 2,679,516 dated March 25, 1954, toDe Groote, with particular reference to columnl8, line 11.

As will be pointed out elsewhere these products as such have utility in various arts although ordinarily color is not a factor. However, if desired these liquid materials can be bleached by the usual procedure using various chars, filtering earth, or chemical bleaching agents, such as peroxides, permanganates, and the like. However, in ordinary practice the materials come through comparatively light in color from a water while to a vary pale straw yellow and thus bleaching is not required.

PART 8 The herein described products may be used for a variety of purposes such as the resolution of petroleum emulsions of the water-in-oil type.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents as, for example,

for cosmetics, spray oils, water-repellent textile finishes;

as lubricants, etc.

So far as the use of the herein described products goes for the purpose of resolving petroleum emulsionsof the Water-in-oil type, and also for that matter for numerous other purposes where surface-active materials are effective, and particularly for those uses specified elsewhere herein, it is preferred to employ oxyalkyla-ted derivatives which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have suflrcient hydrophile character to meet at least the test set forth emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity,

The above mentioned test, i. e., a conventional emulsifiability test, simply means the preferred product for demulsification is soluble in a solvent having hydrophobe properties or in an oxygenated water-insoluble solvent, or even in a mixture containinga fraction of a watersoluble oxygenated hydrocarbon solvent, and that when shaken with water the product may remain in the nonaqueous solvent or, for that matter, it may pass into the aqueous solvent. In other words, although it is xylene soluble, for example, it may also be water soluble to an equal or greater degree. pounds that meet the above test so far as demulsification is concerned, i. e., are soluble in xylene or in a suitable solvent and producean emulsion, have another unusual characteristic; when such compounds or cogeneric mixtures are shaken with one to five or ten times their volume of distilled water in absence of any solvent, the product simply curds out, i. e., does not dissolve in water but seems to hydrate rapidly so as to give a moist curd, i. e., a water-insoluble hydrated precipitate. Of all products tested for demulsifiers, these particular species of the curd or insoluble product. This test is performedwith distilled water at ordinary room temperature, for instance,

225 C. or thereabouts. This cogeneric mixture will be characterized as a hydrophile curd forming product 1 or equivalent.

As has been noted previously the glycols derived in the manner described may be used as such for breaking" They also petroleum emulsions of the water-in-oil type. can be converted into derivatives of the kind subsequently described which also may be used for this same purpose.

Such derivatives are useful for other purposes including the same purpose for which the herein described products are effective. The herein described products may be used for various purposes where detergents, common solvents,

emulsifiers, and the like are used. They may be used as lubricants and as additives to fluids used in hydraulic brake systems; they may be used as emulsifying agents to emulsify or remove greases or dirt; they may be used in the manufacture of a variety of other materials such as isopropyl ether, and glycidyl phenyl ether.

Furthermore, such products may be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an amine,

one may employ what is a somewhat equivalent material,

to wit, a dialkylaminepoxypropane of the structure wherein 'R' and R are alkyl groups.

The products may be combined with carboxy acids such as higher fatty acids so as to change their characteristics .or with polycarboxy acids, .suchas diglycolic, maleic .sources other than petroleum.

However, some of the combroad class of preferred demuls'ifying agents appear to be the best. Therefore, in the hereto appended claims although we have characterized those which meet the conventional emulsification test, we also have characterized this additional class by saying that the solvent-free product, i. e., the cogeneric mixture, when shaken with 2- to 10 times its weight of water curds outas a hydrated Attention is directed to the fact that the'compounds herein described may or may not have definite effective A quick test will reveal that a emulsifying properties. number of them produce emulsions by solution in xylene followed by shaking with water as'previously described.

Over and above this, one sub-specie of the emulsifying species are those which dissolve in xylene and'produce an emulsion but are additionally characterized by the fact that they do not dissolve in water but hydrate in water to give a water-insoluble precipitate generally having the appearance of a floc or flocculent curd or curd which obviously is hydrated and usually highly hydrated.

This particular specie or sub-specie not only has. utility for the purpose mentioned in regard to the class of materials Particular reference is made to five such uses for such more narrow as a whole but also has additional uses.

class.

2,553,183, dated May 15, 1951, to Caron et al.

v be used in substantially the same proportions or lower proportions and this is particularly true when used in conjunction with a glyoxalidine, or amido glyoxalidine..

An analogous use in which these products are equally 25 satisfactory is that described in U. S. Patent No. 2,665,978, dated January 12, 1954, to Stayner et al. The amount employed is in the same proportion or lesser amounts than referred to in said aforementioned Caron et al patent.

The second use is for the purpose of inhibiting fogs in hydrocarbon products as described in U. S. Patents Nos. 2,550,981 and 2,550,982, both dated May 1, 1951, and both to Eberz. Here, again, it can be, used in the same proportions as herein indicated or even small proportions.

A third use is to replace oil soluble petroleum sulfonantes, so-called mahogany soaps, in the preparation of certain emulsions or soluble oils or emulsifiable lubricants where such mahogany soaps are employed. The cogeneric mixtures having this peculiar property serve to replace all or a substantial part of the mahogany soap.

Another use is where the product does not serve as an emulsifying'agent alone but serves as an adjunct.

Briefly stated, the fourth use is concerned with use as a coupling agent to be employed with an emulsifying agent. See The Composition and Structure of Technical Emulsions, J. H. Goodey, Roy. Australian Chem. Inst. J. and Proc., vol. 16, 1949, pp. 47-75. As stated, in the summary of this article, it states The technical oil-in-water emulsion is regarded as a system of four components: the dispersion medium, consisting of the highly polar substance water; the disperse phase composed of hydrocarbons or other substances of comparatively weak polarity; the coupling agent, being an oil-soluble substance involving an hydroxyl, carboxyl or similar polar group; and the emulsifying agent, which is a water-soluble substance involving an hydrocarbon radical attached to an ionizable group.

Thus, these peculiar products giving curdy precipitates with water are unusually effective as coupling agents in many instances.

Fifth, these materials have particular utility in increasing the yield of an oil well by various procedures which in essence involve the use of fracturing of the strata by means of liquid pressure. A mixture of these products with oil or oil in combination with a gel former alone or a gel former and finely divided mineral particles, yields a product which, when it reaches crevices in the strata which are yielding water, forms a gelatinous mass of curdy precipitate or solid or semi-solid emulsion of a 'high viscosity. In any event it represents a rapid gelling agent for the strata crevices and permits pressure to be applied to fracture the strata without loss of fluid through crevices, openings or the like.

The herein described products and the derivatives thereof are particularly valuable in flooding processes for recovery of oil from subterranean oil-bearing strata when employed in the manner described in U. S. Patent No. 2,233,381 dated February 25, 1941, to De Groote and Keiser.

Furthermore, the herein described products may be employed to increase operating efliciency by increasing the oil-to-brine ratio or by increasing the total oil recovery in primary recovery operations as differentiated from secondary recovery operations. The procedures employed are essentially those as described in either U. S. Patent No. 2,331,594, dated October 12, 1943, to Blair, or U. S. Patent No. 2,465,237 dated March 22, 1949, to Larsen.

The herein described compounds of the esters thereof, particularly the higher fatty acid esters, furnish types of emulsifying agents which will serve functionally in two different ways as, for example, either as a primary emulsifier or as a secondary emulsifier as described in U. S. Patent 2,695,877 dated November 30, 1954, to Nichols et a1.

Having thus described our invention what we claim as new and desire to secure by Letters Patent, is

1. A cogeneric mixture of oxyalkylation derivatives of hydroxyl group is tertiary and the other hydroxyl group is not tertiary, and its low stage oxyethylation addition products; said glycols having not over 22 carbon atoms; said low stage oxyethylation step involving .not more than 4 moles of ethylene oxide per mole of glycol, followed by conversion into a surface active mixture; said conversion into a surface active mixture being by virtue of a first stage oxyalkylation involving (a) at least one member of the class consisting of propylene oxide and butylene oxide to provide an intermediate and a second stage oxyalkylation involving (b) ethylene oxide; said intermediate prior to oxyethylation being characterized by water insolubility; said final product being characterized by the fact that hydrophobe property of the intermediate is offset to a signficant degree by the final stage oxyethylation; the average molecular weight of said cogeneric mixture being not over 10,000, and not less than 400.

2. The composition of claim 1 with the proviso that the average molecular weight be not over 8000.

3. The composition of claim 1 with the proviso that the average molecular weight be not over 6000.

4. The composition of claim 1 with the proviso that the average molecular weight be not over 4000.

5. The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000;

6. The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 14 carbon atoms.

7. The composition of claim 1 with the proviso that the average molecularweight be not over 4000 but not less than 1000, with the added proviso that theinitial glycol has not over 12 carbon atoms.

8. The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 10 carbon atoms.

9. The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 10 carbon atoms with the further proviso that such composition is derived from the glycol without initial oxyethylation.

10. The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 10 carbon atoms with the further proviso that such composition is derived from the glycol without initial oxyethylation, and by use of propylene oxide exclusively in the intermediate stage.

11. The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 10 carbon atoms with the further proviso that such composition is derived from the glycol without initial oxyethylation, and by use of propylene oxide exclusively in the intermediate stage; and with the final proviso that said oxypropylated intermediate be water insoluble.

12. The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 10 carbon atoms with the further proviso that such composition is derived from the glycol without initial oxyethylation, and by use of propylene oxide exclusively in the intermediate stage; and with the final proviso that said oxypropylated intermediate be water insoluble and xylene soluble.

13 The composition of claim 1 with the proviso that the average molecular weight be not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 10 carbon atoms with the further a member of the class consisting of glycols in which one 15 proviso that such composition is derived from the glycol a 27 a a without initial oxyethylation, and by use of propylene oxide exclusively in the intermediate stage; and with the final proviso that said, oxypropylated intermediate be water insoluble and xylene soluble, and furthermore that the final product be at least Water miscible.

14. The composition of claiml with the proviso that the average molecular weight be 'not over 4000 but not less than 1000, with the added proviso that the initial glycol has not over 10 carbon atoms, with the further proviso that such composition is derived from the glycol without initial oxyethylation, and by use of propylene oxide exclusively in the intermediate stage; and with the final proviso that said oxypropylated intermediate be water insoluble and xylene soluble, and furthermore that the final product be at least water soluble in distilled Water .at room temperature in a 1% to 5% solution by weight. a

15. The composition of claim 14 with the proviso that the initial glycol be -OH-CE: H

-43-0115 04,811 ()E 16. The composition of claim 14 with the proviso that the initial glycol be 17. The composition of e1aim'14 with the proviso that and consisting of a mixture of the isomers (3113 (1113 OH (0H)C-CH;;OHzOH-CH=-OCE:

and

I H (IJHQ' $Ha CHa0g-(l]-CHzCHrCH CH OH I References Cited in the file of this patent UNITED STATES PATENTS 2,536,685 Harman et al. Jan. 2, 1951- 2,674,619 Lundsted Apr. 6, '1954 

1. A COGENERIC MIXTURE OF OXYALKYLATION DERIVATIVES OF A MEMBER OF THE CLASS CONSISTING OF GLYCOLS IN WHICH ONE HYDROXYL GROUP IS TERTIARY AND THE OTHER HYDROXYL GROUP IS NOT TERTIARY, AND ITS LOW STAGE OXYETHYLATION ADDITION PRODUCTS; SAID GLYCOLS HAVING NOT OVER 22 CARBON ATOMS; SAID LOW STAGE OXYETHYLATION STEP INVOLVING NOT MORE THAN 4 MOLES OF ETHYLENE OXIDE PER MOLE OF GLYCOL, FOLLOWED BY CONVERSION INTO A SURFACE ACTIVE MIXTURE; SAID CONVERSION INTO A SURFACE ACTIVE MIXTURE BEING BY VIRTUE OF A FIRST STAGE OXYALKYLATION INVOLVING (A) AT LEAST ONE MEMBER OF THE CLASS CONSISTING OF PROPYLENE OXIDE AND BUTYLENE OXIDE TO PROVIDE AN INTERMEDIATE AND A SECOND STAGE OXYALKYLATION INVOLVING (B) ETHYLENE OXIDE; SAID INTERMEDIATE PRIOR TO OXYETHYLATION BEING CHARACTERIZED BY WATER INSOLUBILITY; SAID FINAL PRODUCT BEING CHARACTERIZED BY THE FACT THAT HYDROPHOBE PROPERTY OF THE INTERMEDIATE IS OFFSET TO A SIGNIFICANT DEGREE BY THE FINAL STAGE OXYETHYLATION; THE AVERAGE MOLECULAR WEIGHT OF SAID COGENERIC MIXTURE BEING NOT OVER 10,000, AND NOT LESS THAN
 400. 